FULVALENE TITANIUM AND ZIRCONIUM COMPLEXES - SYNTHESIS AND NMR-STUDY OF PHOSPHANIDO-DERIVATIVES, ALKYL-DERIVATIVES, AND ALKYNYL-DERIVATIVES- X-RAY CRYSTAL-STRUCTURES OF 5H5)(MU-PPH(2)))(2)(MU-(ETA(5)-C5H4-ETA(5)-C5H4))] AND (MU-C-CSUME(3)))(2)(MU-(ETA(5)-C5H4-ETA(5)-C5H4))]

Reaction of 5)-C5H5)(mu-Cl)}(2){mu-{eta(5)-C5H4-eta(5)-C5H4)}] (M = Ti , 1; Zr, 2) or a(5)-C5H5)Cl-2}(2){mu-{eta(5)-C5H4-eta(5)-C5H4)}], (M = Ti, 5; Zr, 6) with one or two equivalents of LiPPh(2) afforded the ne w phosphanidometal(III) complexes [{(M(C5H5)(mu-PPh(2))}(2){mu-(eta(5) -C5H4)}], 5-C,H,))1, (M = Ti, 3; Zr, 4). Reaction of 2 with LiC drop C SiMe(3) led to the diamagnetic zirconium(III) alkynyl derivative [{Zr( C5H5)(mu-C drop CSiMe(3))}(2)(mu-eta(5)-C(5)H4-eta(5)-C5H4], 7. Alkyla tion of 6 with LiCH(2)CMe(2)Ph gave 5)-C5H5)(CH(2)CMe(2)Ph)(2)}(2){mu- (eta(5)-C5H4-eta 5-C5H4)}], 8. A detailed NMR study of complexes 3 and 4 allowed the observation of the spectral behaviour of the eight diff erent fulvalene protons through their coupling to the P-31 nucleus. Th e fluxional behaviour of complex 7 was studied by dynamic DNMR, and ki netic parameters for the sigma-pi-conversion of the alkynyl ligand wer e determined. The molecular structures of complexes 3 and 7 were deter mined by X-ray diffraction methods.